Highly chlorinated nitrogen heterocyclic compounds and process for producing the same



United States Patent M HIGHLY CHLORINATED NITROGEN HETEROCY- CLIC COMPOUNDS AND PROCESS FOR PRO- DUCING THE SAME Hans Holtschmidt and Horst Tarnow, Leverkusen, Germany, assignors to Farbenfabriken Bayer Aktiengesellschaft, Leverkusen, Germany, a corporation of Germany No Drawing. Filed Nov. 1, 1965, Ser. No. 505,963 Claims priority, application geirmany, Dec. 16, 1964,

7 Claims. (Cl. 260319.1)

It has now been found that highly chlorinated S-membered or 6-membered nitrogen heterocyclic compounds can be obtained if aromatic isocyanide dichlorides or imide chlorides which contain a chlorine atom or a chloralkyl group in the o-position to the nitrogen are heated to 250 to 800 C. A large proportion of the starting materials are compounds of the general formula:

R represents hydrogen, chloro, perchlorinated lower alkyl and -N=C-Y R represents hydrogen, chloro, perchlorinated lower alkyl and --N=C-Y R represents hydrogen, chloro, perchlorinated lower alkyl and -N=CY and R represents hydrogen, chloro and perchlorinated lower alkyl, Y in each of N=C-Y being selected from the group consisting of chloro and lower perchlorinated alkyl and at least one of R and R being other than hydrogen.

R R can form a condensed aromatic ring (preferably five and six membered) which itself can again carry the substituents R R and Y represents chlorine and a lower perchlorinated alkyl radical.

01 C1 o on :N-pentachrophenyl-trichloromethyl imide chloride Patented Aug. 8, 1967 (Ill N-pen'tachlorophenyl-pentachloroethyl imide chloride 2,4-dichl0r06-trichloromethylphenylisocyanide dichloride N-[2,3,4,fi-tetrachloro-6-t1'ichl0r0methylphenyl]-trichloromethyl imide chloride C1- -C1Cl5 /Cl C1 :0

2,3,4,5-tetrachloro-6-pent-achloroethylphenyl lsocyanide dichloride [2,3,5,6tetrachlorophenylene-(1,4) ]-bis-trlchl0romethy1 imide chloride [2,4,5,G-tetrachlorophenylene-(1,3) ]-bis-'trichloromethy1 imide chloride Cl (111 N Cl C1 Cl C] Heptachloronaphthyl-l-isocyanide dichloride I 31 Cl N-heptachloronaphthyl-trichloromethyl imide chloride The heating, which causes a pyrolysis reaction, is carried out at temperatures from about 250 to about 800 C.,

advantageously 300 to 600 C., optionally in the presence 7 of an inert organic solvent and optionally in an inert gas atmosphere. The starting material can be heated gradually up to reflux temperature or until chlorine is visibly split off. The reaction period is about 1-10 hours and advantageously 25 hours. However, the molten substance or the substance dissolved in an inert solvent, such as chloroform, carbon tetrachloride, dichlorobenzene, trichloro= benzene and others, can be exposed for a longer residence time in a heated tube. The residence time is for example 1-30 minutes. However, it is also possible to work with shorter residence times and for the product obtained to be again subjected to pyrolysis. In this way, the process can also be carried out continuously, it being possible for some of the reaction material to be conducted in a cycle. In every case, the use of an inert gas such as nitrogen or carbon dioxide is advantageous.

The process is explained by using, as an example, the pyrolysis of pentachlorophenyl trichloromethyl imide chloride.

Cl (31 C1 CO1: 01

l ---v 01 f 01- \N% 01 It is outstanding that readily accessible starting compounds can be transformed under simple conditions into highly chlorinated nitrogen heterocyclic compounds. It is surprising that the distinctlyintrarnolecular reaction proceeds with chlorine being split off, without uncontrolled cracking reactions, and without intrarnolecular condensation reactions. A ring-closure reaction occurs with chlorine or perchloralkane being split off, the imide chlorides or isocyanide dichlorides changing into chlorine-containing nitrogen heterocyclic compounds.

The highly chlorinated nitrogen heterocyclic compounds which'can be produced by the process according to the invention were not previously available or only available with difliculty by other methods. They are valuable products for the preparation of pest control agents, herbicides, dyestuffs and plastics.

The new compounds obtainable according to the invention are valuable intermediates for the production of pestcontrol agents, dyestuifs and plastics.

They have both herbicidal and insecticidal properties and accordingly they can also be directly employed. The highly chlorinated compounds have a particularly strong action against insects such as flies, ticks and cockroaches.

The heptachloroquinoline has a strong insecticidal action. Aqueous emulsions of different concentrations of heptachloroquinoline are prepared by dissolving it in dimethylformamide and diluting the solution with water and a non-ionic emulsifier to the required concentration. Even in a concentration of 0.01%, such emulsions destroy flies, gnats and cockroaches.

The following examples illustrate the invention:

Example 1 430 parts by weight of pentachlorophenyl trichloromethylimide chloride were heated for 8 hours in a weak stream of nitrogen to 380 400 C.

Subsequent vacuum distillation produced 326 parts by weight of perchlorindolenine of the formula:

B.P. 145 C., colourless crystals of M.P.: 122- 124 C.

Analysis for C Cl N-Calculated: 69.31% of total chlorine. Found: 70.40% of total chlorine. Calculated: 29.70% saponifiable chlorine. Found: 29.80% saponifiable chlorine corresponding to 3 chlorine.

Example 2 256 parts by weight of pentachlorophenyl pentachloroethyl imide chloride were heated for 7 hours in a .weak stream of nitrogen to 400 C. The residue which remained was recrystallised from Wash benzine. There were: obtained parts by weight of perchloroquinoline of the formula I Cl Colourless crystals of M.P. ISO-152 C.

Analysis for C Cl N-Calculated: 67.07% chlorine. Found: 67.05% chlorine.

Example 3 parts by weight of 2,4-dichloro-6-trichloromethyl B.P. 100-105 C., 11 1.6160.

Analysis for C H Cl N-Calculated: 61.31% chlorine. Found: 62.70% chlorine.

6 What we claim is: I 01 1. Highly chlorinated nitrogen heterocyclic compounds I of the formula 0146-01 |C O C13 01 N 01 bl 5 l R 01 01 01 01 r and 7 C1. /0-01 01 01 01- 01 in which in which R is defined as R is a member selected from the group consisting of hydrogen chloro and perchlorinated lower alkyl; R is a member selected from the group consisting of hydrogen, chloro, perchlorinated lower alkyl and l N=CY 3. C1

R is a member selected from the group consisting of hydrogen, chloro, perchlorinated lower alkyl and and z is a whole number of 1-4. 2. The compound of the formula 1 being selected from the group consisting of chlorine c1 and perchlorinated lower alkyl and at least one of G1 I 01 R and R being other than hydrogen.

5. The process of claim 4 wherein the heating is carried out at a temperature of from 300600 C. N 6. The process of claim 4, wherein the heating is carried out in the presence of an inert organic solvent.

7. The process of claim 4, wherein the heating is carried 4. A process for the production of highly chlorinated out 111 the Presence of an men nitrogen heterocyclic compounds which comprises heating to 250800 C. a member selected from the g'roupcon- References Cited 35 3. The compound of the formula sisting of UNITED STATES PATENTS 2,661,276 12/1953 Schlesinger 260-283 XR -fi- 2,886,568. 5/1959 Stransbury 61131 260-283 OTHER REFERENCES Holt Schmidt: Angerwandt Chemie, vol. 74, pp. 848- 55 (November 1962). R -N=0Y. 01 01 I I ALEX MAZEL, Primary Examiner. t C DONALD G. DAUS, Assistant Examiner. 

1. HIGHLY CHLORINATED NITROGEN HETEROCYCLIC COMPOUNDS OF THE FORMULA
 4. A PROCESS FOR THE PRODUCTION OF HIGHLY CHLORINATED NITROGEN HETEROCYCLIC COMPOUNDS WHICH COMPRISES HEATING TO 250-800*C. A MEMBER SELECTED FROM THE GROUP CONSISTING OF 